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US6391255B1 - Metallurgical-grade silicon with a controlled structure for use in halosilane synthesis - Google Patents

Metallurgical-grade silicon with a controlled structure for use in halosilane synthesis Download PDF

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Publication number
US6391255B1
US6391255B1 US09/155,343 US15534399A US6391255B1 US 6391255 B1 US6391255 B1 US 6391255B1 US 15534399 A US15534399 A US 15534399A US 6391255 B1 US6391255 B1 US 6391255B1
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Prior art keywords
silicon
aluminum
ppm
metallurgical
primary
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US09/155,343
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English (en)
Inventor
Thomas Margaria
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Ferroglobe France SAS
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Pechiney Electrometallurgie SAS
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Assigned to PECHINEY ELECTROMETALLURGIE reassignment PECHINEY ELECTROMETALLURGIE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MARGARIA, THOMAS
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • C01B33/025—Preparation by reduction of silica or free silica-containing material with carbon or a solid carbonaceous material, i.e. carbo-thermal process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis

Definitions

  • the invention relates to a particular quality of metallurgical silicon with a controlled structure and containing aluminum, intended particularly for synthesis of alkyl or aryl-halogenosilanes used in the manufacture of silicones.
  • Metallurgical silicon is silicon obtained industrially by carbothermal reduction of silica in an electric furnace. It contains at least 98% silicon, and the other main elements are iron, aluminum and calcium. It also contains some oxygen and other elements such as P, Ti, V, Ni, etc., with a content of ⁇ 0.1%.
  • Rochow's reaction has been developed industrially to a large extent because it is the basis of the silicones industry. It is usually used with methyl chloride CH 3 Cl and gives a mix of different methyl chlorosilanes, particularly monomethyl-trichlorosilane (denoted by the letter T) and dimethyl-dichlorosilane (denoted by D). Since the required product is D, it is important to carry out the reaction so that a maximum proportion of D is obtained in the resulting mix of silanes, this proportion being called the selectivity of the reaction. It is also important to produce the maximum quantity of silanes per unit time, the value of the weight of silanes produced per unit time being called the reactivity.
  • the applicant looked for a means of improving the reactivity and selectivity of the reaction by acting on the silicon grains themselves. This can be done by checking their phosphorus content, as described in WO 95/01303 deposited by BAYER and the applicant.
  • the silicones industry continues to require silicon capable of further increasing the selectivity and reactivity of the Rochow reaction.
  • the object of the invention is a metallurgical silicon intended to be used for the synthesis of alkyl and aryl halogenosilanes, the structure of which is composed of primary silicon crystals and intermetallic compounds based essentially on silicon, iron, aluminum and calcium, and is characterized in that more than 90% of the primary silicon grains have an aluminum content of between 50 and 1000 ppm.
  • This structure is preferably obtained with a silicon with a global aluminum content by weight of between 0.12 and 0.30%, and with a silicon solidification process after casting capable of dropping below 1200° C. in less than 10 seconds.
  • the applicant has found that for a given range of aluminum contents and under particular conditions for solidification of the liquid silicon, it is possible to increase the aluminum content of the primary silicon crystals beyond the normal saturation limit of 15 ppm, and to control the super-saturation level by adjusting the content of aluminum in the liquid silicon and its solidification rate, in order to increase the reactivity of silicon in the Rochow reaction.
  • SIMS Single Ion Mass Spectrometry
  • This RSF factor is obtained by taking the average of at least five measurements made on pre-implanted standards with a known concentration, and is of the order of 3.3 10 23 .
  • the super-saturation level of aluminum in primary silicon increases with the aluminum content in the initial liquid silicon and with the solidification rate.
  • 4 mm thick silicon is cast on a water cooled copper plate, resulting in complete solidification in less than 10 seconds, the following values are obtained (by weight):
  • the cooling rate particularly between 1400 and 1200° C., also affects the percentage of primary silicon crystals with an aluminum content exceeding 50 ppm, very high rates giving more than 95% of super-saturated crystals, or even percentages close to 100%.
  • a liquid silicon with the following composition (by weight) is a liquid silicon with the following composition (by weight)
  • This silicon was then refined in the ladle by the addition of silica and the injection of oxygen to lower the Ca and Al contents.
  • the analysis of the refined silicon was as follows:
  • the tests were carried out in a 30 mm diameter glass reaction vessel with stirred bed, equipped with a stirrer.
  • the same quantity of silicon was used in each test, with the same distribution of particles between 70 and 160 ⁇ m.
  • the reaction mix consisted of 40 g of silicon, 3.2 g of partially oxidized copper as a catalyst and 0.05 g of ZnO.
  • Methyl chlorine was added to the reaction mix through a sintered glass disk at a pressure of 0.2 MPa. After heating the reaction medium and starting the reaction, the system temperature was adjusted and kept at 300° C. and the quantity and composition of the silanes mix formed was determined.
  • sample 1 in which the primary silicon is super-saturated in aluminum, has a 6% better reactivity while the selectivity has only changed by 0.2%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
US09/155,343 1996-04-02 1997-03-24 Metallurgical-grade silicon with a controlled structure for use in halosilane synthesis Expired - Fee Related US6391255B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9604378A FR2746785B1 (fr) 1996-04-02 1996-04-02 Silicium metallurgique a structure controlee destine a la synthese des halogenosilanes
FR9604378 1996-04-02
PCT/FR1997/000514 WO1997036821A1 (fr) 1996-04-02 1997-03-24 Silicium metallurgique a structure controlee destine a la synthese des halogenosilanes

Publications (1)

Publication Number Publication Date
US6391255B1 true US6391255B1 (en) 2002-05-21

Family

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US09/155,343 Expired - Fee Related US6391255B1 (en) 1996-04-02 1997-03-24 Metallurgical-grade silicon with a controlled structure for use in halosilane synthesis

Country Status (5)

Country Link
US (1) US6391255B1 (fr)
EP (1) EP0891297A1 (fr)
AU (1) AU2298397A (fr)
FR (1) FR2746785B1 (fr)
WO (1) WO1997036821A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050074388A1 (en) * 2001-07-23 2005-04-07 Gerard Baluais Medium purity metallurgical silicon and method for preparing same
JP2016172743A (ja) * 2009-10-16 2016-09-29 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ オルガノハロシランの製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2380995A (en) * 1941-09-26 1945-08-07 Gen Electric Preparation of organosilicon halides
US5068385A (en) * 1989-09-08 1991-11-26 Bayer Aktiengesellschaft Process for the preparation of alkyl halogenosilanes
US5182091A (en) * 1990-05-30 1993-01-26 Kawasaki Steel Corporation Method and apparatus for purifying silicon
EP0673880A1 (fr) * 1994-02-25 1995-09-27 Pechiney Electrometallurgie Silicium métallurgique à microstructure contrôlée pour la préparation des halogénosilanes
US5714131A (en) * 1993-07-01 1998-02-03 Pechiney Electrometallurgie Metallurgical silicon containing phosphorus for the preparation of organohalogenosilanes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO169831C (no) * 1989-11-22 1993-06-08 Elkem As Silisiumprodukt for bruk ved fremstilling av organosilaner og klorsilaner samt fremgangsmaate for fremstilling av silisiumprodukt.
DE4303766A1 (de) * 1993-02-09 1994-08-11 Wacker Chemie Gmbh Verfahren zur Herstellung von Methylchlorsilanen
AU669255B2 (en) * 1993-03-24 1996-05-30 Ge Bayer Silicones Gmbh & Co. Kg Process for the preparation of organochlorosilanes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2380995A (en) * 1941-09-26 1945-08-07 Gen Electric Preparation of organosilicon halides
US5068385A (en) * 1989-09-08 1991-11-26 Bayer Aktiengesellschaft Process for the preparation of alkyl halogenosilanes
US5182091A (en) * 1990-05-30 1993-01-26 Kawasaki Steel Corporation Method and apparatus for purifying silicon
US5714131A (en) * 1993-07-01 1998-02-03 Pechiney Electrometallurgie Metallurgical silicon containing phosphorus for the preparation of organohalogenosilanes
EP0673880A1 (fr) * 1994-02-25 1995-09-27 Pechiney Electrometallurgie Silicium métallurgique à microstructure contrôlée pour la préparation des halogénosilanes
US5605583A (en) * 1994-02-25 1997-02-25 Pechiney Electrormetallurgie Metallurgical silicon with controlled microstructure for the preparation of halogenosilanes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050074388A1 (en) * 2001-07-23 2005-04-07 Gerard Baluais Medium purity metallurgical silicon and method for preparing same
US7404941B2 (en) * 2001-07-23 2008-07-29 Ferropem Medium purity metallurgical silicon and method for preparing same
JP2016172743A (ja) * 2009-10-16 2016-09-29 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ オルガノハロシランの製造方法

Also Published As

Publication number Publication date
WO1997036821A1 (fr) 1997-10-09
AU2298397A (en) 1997-10-22
FR2746785A1 (fr) 1997-10-03
EP0891297A1 (fr) 1999-01-20
FR2746785B1 (fr) 1998-05-22

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Effective date: 19981207

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Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

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Effective date: 20060521

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